Radiation Sources and Spectrometers

Fig. 3.19 Schematic illustration of the measurement geometry for Mossbauer spectrometers. In transmission geometry, the absorber (sample) is between the nuclear source of 14.4 keV y-rays (normally Co/Rh) and the detector. The peaks are negative features and the absorber should be thin with respect to absorption of the y-rays to minimize nonlinear effects. In emission (backscatter) Mossbauer spectroscopy, the radiation source and detector are on the same side of the sample. The peaks are positive features, corresponding to recoilless emission of 14.4 keV y-rays and conversion X-rays and electrons. For both measurement geometries Mossbauer spectra are counts per channel as a function of the Doppler velocity (normally in units of mm s relative to the mid-point of the spectrum of a-Fe in the case of Fe Mossbauer spectroscopy). MIMOS II operates in backscattering geometry circle), but the internal reference channel works in transmission mode...

A typical IR spectrometer consists of the following components radiation source, sampling area, monochromator (in a dispersive instrument), an interference filter or interferometer (in a non-dispersive instrument), a detector, and a recorder or data-handling system. The instrumentation requirements for the mid-infrared, the far-infrared, and the near-infrared regions are different. Most commercial dispersive infrared spectrometers are designed to operate in the mid-infrared region (4000-400 cm ). An FTIR spectrometer with proper radiation sources and detectors can cover the entire IR region. In this section, the types of radiation sources, optical systems, and detectors used in the IR spectrometer are discussed. 

An absorption spectrometer requires a separate radiation source and a sample compartment that holds containers for the sample and blank. With an emission spectrometer, the sample is introduced directly into a hot plasma or flame where excitation and emission occur. 

Fiber optics may be used as probes for conventional spectrophotometric and fluorescence measurements. Light must be transmitted from a radiation source to the sample and back to the spectrometer. While there are couplers and designs that allow light to be both transmitted and received by a single fiber, usually a bifurcated fiber cable is used. This consists of two fibers in one casing, split at the end that goes to the radiation source and the spectrometer. Often, the cables consist of a bundle of several dozen small fibers, and half are randomly separated from the other at one end. For absorbance measurements, a small mirror is mounted (attached to the cable) a few millimeters from the end of the fiber. The source radiation penetrates the sample solution and is reflected back to the fiber for collection and transmission to the spectrometer. The radiation path length is twice the distance between the fiber and the mirror. 

The basic concepts of atomic absorption spectrometry were published first by Walsh in 1955, this can be regarded as the actual birth year of the technique. At the same time Alkemade and Milatz designed an atomic absorption spectrometer in which flames were employed both as a radiation source and an atomizer. The commercial manufacture of atomic absorption instruments, however, did not start until ten years later. Since then the development of atomic absorption spectrometry has been very fast, and atomic absorption (AA) instruments very quickly became common. The inventions of dinitrogen oxide as oxidant and electrothermal atomization methods have both significantly expanded the utilization field of atomic absorption spectrometry. These techniques increased the number of measurable elements and lowered detection limits. Todays graphite furnace technique is based on the studies of King at the beginning of the twentieth century. 

In order to make the lamp change rapid, various arrangements are offered by the manufacturers. For instance, by a ferris-wheel like turret a sequence of elements can be measured during each turret rotation. Another approach is a combination of a continuum radiation source and a high-resolution spectrometer. However, this combination has not achieved great acceptance. A common problem with continuum sources is their relatively low intensity in the UV region. 

The first commercial plasma atomic fluorescence spectrometer was developed by Demers and Allemand. Hollow cathode lamps are used as radiation sources and an inductively coupled plasma torch as an atomizer. Detection limits are reported for more than 30 elements. The linear dynamic range is normally 10 to 10. ... 

The IR spectrum of a compound can easily be obtained in a few minutes. A small sample of the compound is placed in an instrument with an IR radiation source. The spectrometer automatically scans the amount of radiation that passes through the sample over a given frequency range and records on a chart the percentage of radiation that is transmitted. Radiation absorbed by the molecule appears as a band in the spectrum. 

The third unit, besides the radiation source and the spectrometer, including the detector, is the instrument control including the operator surface, which is shown in Figure 3.17. The optimum measurement conditions are checked for each spectral range and adjusted before each measurement within a few milliseconds. When the full capability of the system is utilized, a complete set of data from 576 simultaneously read pixels is obtained per millisecond during data evaluation. The data are pre-averaged and the averaged data are transmitted to the application software. 

In commercial PA spectrometers, incoherent sources such as lamps are employed in combination with filters or with an interferometer. Devices equipped with a small light bulb, with either a chopper or direct current modulation as modulated radiation source and appropriate filters to avoid absorption... 

Fig. 35. 3p doublet electron lines from Ar gas studied by means of Nel radiation. Light source and spectrometer adjusted for max resolving power of 5.7 meV. 

Spectrometers are designed to measure the absorption of electromagnetic radiation by a sample. Basically, a spectrometer consists of a source of radiation, a compartment containing the sfflnple through which the radiation passes, and a detector. The frequency of radiation is continuously varied, and its intensity at the detector is compar ed with that at the source. When the frequency is reached at which the sample absorbs radiation, the detector senses a decrease in intensity. The relation between frequency and absorption is plotted as a spectrum, which consists of a series of peaks at characteristic frequencies. Its interpretation can furnish structural information. Each type of spectroscopy developed independently of the others, and so the data format is different for each one. An NMR spectrum looks different from an IR spectrum, and both look different from a UV-VIS spectrum. 

Plasma sources were developed for emission spectrometric analysis in the late-1960s. Commercial inductively coupled and d.c. plasma spectrometers were introduced in the mid-1970s. By comparison with AAS, atomic plasma emission spectroscopy (APES) can achieve simultaneous multi-element measurement, while maintaining a wide dynamic measurement range and high sensitivities and selectivities over background elements. As a result of the wide variety of radiation sources, optical atomic emission spectrometry is very suitable for multi-element trace determinations. With several techniques, absolute detection limits are below the ng level. 

In a typical MIP-MS instrument, the ICP portion is replaced with one of a variety of microwave discharge sources, usually a fairly standardised (modified) Beenakker cavity connected to a microwave generator. The analytical MIP at intermediate power (<500 W) is a small and quiet plasma source compared with the ICP. The mass spectrometer needs no major modifications for it to be interfaced with the MIP. With MIP used as a spectroscopic radiation source, typically consisting of a capillary (1mm i.d.), a power of 30-50 W and a gas flow below 1 L min 1, multi-element determinations are possible. By applying electrodeposition on graphite electrodes, ultratrace element determinations are within reach, e.g. pg amounts of Hg. 

Consequently, mirror optics are more common, in particular in the mid-IR. The mirrors used are usually aluminium- or gold-coated flat or curved substrates. While near-IR mirrors are usually protected by thin SiO-layers, in the mid-IR unprotected mirrors have to be used. Disadvantages of mirror optics are the elevated space consumption and the higher prices in comparison to refractive optics, especially comparing non-standard mirrors against non-standard lens. In total, mirror optics are so preferable to fibres and refractive optics, at least in the mid-IR, that in some technical applications they are used to replace waveguides to transport IR radiation between source, sensor head and spectrometer. 

Modem instrumentation has improved substantially in recent years, which has enabled the measurement of XPS spectra of superior resolution necessary to reveal the small BE shifts present in highly covalent compounds such as those studied here. In a laboratory-based photoelectron spectrometer, a radiation source generates photons that bombard the sample, ejecting photoelectrons from the surface that are transported within a vacuum chamber to a detector (Fig. 2). The vacuum chamber is required to minimize the loss of electrons by absorption in air and, if a very high quality vacuum environment is provided (as is the case with modem instruments), the surface contamination is minimized so that the properties of the bulk material are more readily determined. 

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